JPS6323184B2 - - Google Patents

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Publication number
JPS6323184B2
JPS6323184B2 JP58231624A JP23162483A JPS6323184B2 JP S6323184 B2 JPS6323184 B2 JP S6323184B2 JP 58231624 A JP58231624 A JP 58231624A JP 23162483 A JP23162483 A JP 23162483A JP S6323184 B2 JPS6323184 B2 JP S6323184B2
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JP
Japan
Prior art keywords
reaction
cesium
nitrodiphenylamine
copper
rubidium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
JP58231624A
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Japanese (ja)
Other versions
JPS59112947A (en
Inventor
Biri Myuraa Erunsuto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of JPS59112947A publication Critical patent/JPS59112947A/en
Publication of JPS6323184B2 publication Critical patent/JPS6323184B2/ja
Granted legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J27/26—Cyanides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C07C211/55—Diphenylamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C07C211/56—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Description

【発明の詳細な説明】 本発明は炭酸カリウム及び銅化合物の存在下に
おける４−ニトロハロゲンベンゼンと第一級芳香
族アミンとの反応による４−ニトロジフエニルア
ミンの製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing 4-nitrodiphenylamine by reaction of 4-nitrohalogenbenzene with a primary aromatic amine in the presence of potassium carbonate and a copper compound.

ハロゲンニトロベンゼンと芳香族アミンとの反
応は長い期間公知のものであつた。かくして、触
媒として炭酸アルカリ及び銅化合物の存在下にて
反応を行うことはドイツ特許第185663号から公知
のものである。 The reaction of halogen nitrobenzenes with aromatic amines has been known for a long time. It is thus known from DE 185 663 to carry out the reaction in the presence of an alkali carbonate and a copper compound as catalysts.

更に、炭酸カリウムを加え、そして反応の水を
共沸蒸留により除去した場合、極めて遅い反応が
加速化され得ることが公知である。米国特許第
2927943号の実施例１により、かなり純粋な４−
ニトロジフエニルアミンがこれらの条件下で21時
間にわたつて理論収率の73％の収率で得られる。
更に、ハロゲンニトロベンゼンと第一級芳香族ア
ミンとの反応中に、還元的脱ハロゲン化によるニ
トロベンゼンの生成の如き（米国特許第3313854
号の第３欄、64及び65行目参照）大量のタール及
び副生物の生成による汚染が反応時間を長くする
欠点を与えることが米国特許第4155936号から公
知である。 Furthermore, it is known that very slow reactions can be accelerated if potassium carbonate is added and the water of reaction is removed by azeotropic distillation. US Patent No.
According to Example 1 of No. 2927943, fairly pure 4-
Nitrodiphenylamine is obtained under these conditions in a yield of 73% of theory over 21 hours.
Furthermore, during the reaction of halogen nitrobenzene with primary aromatic amines, such as the formation of nitrobenzene by reductive dehalogenation (U.S. Pat. No. 3,313,854)
It is known from US Pat. No. 4,155,936 that contamination due to the formation of large amounts of tar and by-products has the disadvantage of prolonging the reaction time.

これらの欠点を克服するために、反応混合物に
対する共触媒として極性溶媒が加えられている。
しかしながら、現在まで使用されてきた極性溶媒
はすべて欠点も有するものである。かくして、米
国特許第3055940号により使用されるジメチルホ
ルムアミドは反応条件下で揮発性であり、そして
このものは容易に分離し得る副生物を生成しな
い。米国特許第3055940号により使用されるヘキ
サメチルリン酸トリアミド、及び米国特許第
3313854号により使用されるホルムアニリドは銅
化合物の存在下において触媒的量で不満足な程度
でのみ加速特性を有している。米国特許第
3277175号、ドイツ特許出願公告第1518307号及び
同第1117594号により使用されるジメチルスルホ
キシド、アセトアニリド及びサリチルアニリドも
わずかな効果のみを示す。またこれはドイツ特許
出願公開第2633811号によるＮ−メチルピロリド
ン、または日本特許第56／022751号によるε−カ
プロラクタムに応用されている。 To overcome these drawbacks, polar solvents have been added as cocatalysts to the reaction mixture.
However, all the polar solvents used to date also have drawbacks. Thus, the dimethylformamide used according to US Pat. No. 3,055,940 is volatile under the reaction conditions and it does not produce easily separable by-products. Hexamethyl phosphate triamide as used by U.S. Pat. No. 3,055,940 and U.S. Pat.
The formanilide used according to No. 3,313,854 has acceleration properties only to an unsatisfactory extent in catalytic amounts in the presence of copper compounds. US Patent No.
Dimethyl sulfoxide, acetanilide and salicylanilide used according to DE 3277175, DE 1518307 and DE 1117594 also show only a slight effect. It has also been applied to N-methylpyrrolidone according to German Patent Application No. 2633811 or to ε-caprolactam according to Japanese Patent No. 56/022751.

米国特許第4155936号に記載されたポリエーテ
ルの添加も欠点を有している。処理方法に依存し
て、添加物が目的生成物中または排水中に残留す
る。 The addition of polyethers as described in US Pat. No. 4,155,936 also has drawbacks. Depending on the treatment method, additives remain in the target product or in the waste water.

タールの生成を減少させる他の可能性として米
国特許第3121736号はアミノカルボン酸、アルキ
ルジアミノポリカルボン酸及びその塩、ジサルチ
ルアルジアミノアルカン、ｏ−ヒドロキシベンザ
ルアミノフエノール、ポリホスフエート、カルボ
キシメチルメルカプトコハク酸またはサリチルア
ルデヒドのシツフ塩基の添加を推奨している。 Other possibilities for reducing tar formation include aminocarboxylic acids, alkyldiaminopolycarboxylic acids and their salts, disaltylardiaminoalkanes, o-hydroxybenzalaminophenols, polyphosphates, carboxymethylmercaptosuccines. The addition of a Schiff base of acid or salicylaldehyde is recommended.

これらの物質を用いる場合、処理工程で問題が
生じる。 When using these materials, problems arise in the processing process.

今や、炭酸カリウム及び銅化合物の存在下にて
式（） 式中、R1及びR2は同一または相異なるもので
あり、且つ水素または炭素原子１〜９個を有する
アルキル基を表わし、そしてＸは塩素または臭素
を表わす、 に対応するハロゲンニトロベンゼンと式（） 式中、R3及びR4は式（）におけるR1及びR2
と同様の意味を有する、 に対応する第一級芳香族アミンとの反応による式
（） 式中、R1、R2、R3及びR4は上記の通りであ
る、 に対応する４−ニトロジフエニルアミンの製造に
対する方法が見い出され、その際にルビジウムも
しくはセシウム化合物またはその２つの混合物を
加えることにこの方法の特徴がある。 Now, in the presence of potassium carbonate and copper compounds the formula () In the formula, R 1 and R 2 are the same or different and represent hydrogen or an alkyl group having 1 to 9 carbon atoms, and X represents chlorine or bromine. ) In the formula, R 3 and R 4 are R 1 and R 2 in formula ()
The formula () by reaction with a primary aromatic amine corresponding to has the same meaning as A process has now been found for the preparation of 4-nitrodiphenylamine corresponding to the formula in which R 1 , R 2 , R 3 and R 4 are as defined above, wherein a rubidium or cesium compound or a mixture of the two is used. The feature of this method is that it adds

式（）に対応するアルキル基として炭素原子
１〜３個を有するアルキル基が好適に含まれる。 The alkyl group corresponding to formula () preferably includes an alkyl group having 1 to 3 carbon atoms.

４−ニトロクロロベンゼン及びアニリンからの
４−ニトロジフエニルアミンの製造方法が好適に
使用される。 A method for producing 4-nitrodiphenylamine from 4-nitrochlorobenzene and aniline is preferably used.

次のものが本発明の方法に使用し得る銅触媒の
例として挙げられる：ヨウ化銅（）、塩化銅
（）、塩化銅（）、臭化銅（）、臭化銅（）、
シアン化銅（）、酸化銅（）、酸化銅（）、
炭酸銅（）、塩基性炭酸銅（）、硫酸銅（）、
硝酸銅（）、ギ酸銅（）、酢酸銅（）並びに
一価または二価の銅の有機及び無機配位化合物。
含酸素銅化合物、例えば酸化銅（）、炭酸銅
（）、塩基性炭酸銅または酸化銅（）が好まし
く、その際に用いるハロゲンニトロベンゼン１モ
ル当り0.001〜0.1、好ましくは0.01〜0.05モルの
量で銅触媒を加える。この銅触媒はそれ自身で
か、または一緒に混合して用いることができる。 The following may be mentioned as examples of copper catalysts that can be used in the process of the invention: copper iodide (), copper chloride (), copper chloride (), copper bromide (), copper bromide (),
Copper cyanide (), copper oxide (), copper oxide (),
Copper carbonate (), basic copper carbonate (), copper sulfate (),
Copper nitrate (), copper formate (), copper acetate () and monovalent or divalent organic and inorganic coordination compounds of copper.
Oxygenated copper compounds, such as copper oxide (), copper carbonate (), basic copper carbonate or copper oxide () are preferred, in an amount of 0.001 to 0.1, preferably 0.01 to 0.05 mol, per mole of halogen nitrobenzene used. Add copper catalyst. The copper catalysts can be used on their own or mixed together.

ハロゲンニトロベンゼンの例として次のものが
含まれる：４−ニトロクロロベンゼン、４−ニト
ロブロモベンゼン、４−ニトロ−２−メチル−ク
ロロベンゼン及び４−ニトロ−３−メチル−クロ
ロベンゼン。 Examples of halogen nitrobenzenes include: 4-nitrochlorobenzene, 4-nitrobromobenzene, 4-nitro-2-methyl-chlorobenzene and 4-nitro-3-methyl-chlorobenzene.

第一級芳香族アミンの例として次のものが含ま
れる：アニリン、ｏ−トルイジン、ｍ−トルイジ
ン、ｐ−トルイジン、４−エチルアニリン、４−
ブチルアニリン、４−イソプロピルアニリン、
３，５−ジメチルアニリン及び２，４−ジメチル
アニリン。 Examples of primary aromatic amines include: aniline, o-toluidine, m-toluidine, p-toluidine, 4-ethylaniline, 4-
Butylaniline, 4-isopropylaniline,
3,5-dimethylaniline and 2,4-dimethylaniline.

勿論、芳香族アミンは混合物、殊に異性体混合
物の状態でも用いることができる。一般にハロゲ
ンニトロベンゼン１モル当り約１〜６モル、好ま
しくは1.5〜３モル、そして殊に1.7〜2.5モルの芳
香族アミンを用いる。 Of course, the aromatic amines can also be used in the form of mixtures, especially isomeric mixtures. Generally about 1 to 6 moles, preferably 1.5 to 3 moles, and especially 1.7 to 2.5 moles of aromatic amine are used per mole of halogen nitrobenzene.

ルビジウムまたはセシウム化合物として例えば
次のものが含まれる：塩化物、臭化物、ヨウ化
物、硫酸塩、酸化物、水酸化物、炭酸塩、炭酸水
素塩、ギ酸塩、酢酸塩、プロピオン酸塩、シアン
化物及びリン酸塩、並びにその混合物、しかし殊
に弱い有機または無機酸の塩、例えば炭酸塩、酢
酸塩、ギ酸塩及びシアン化物。セシウム化合物が
好ましい。使用される塩は反応容器中にて水酸化
物及び対応する酸からか、または適当な酸誘導体
から生成することができる。 Rubidium or cesium compounds include, for example: chloride, bromide, iodide, sulfate, oxide, hydroxide, carbonate, bicarbonate, formate, acetate, propionate, cyanide. and phosphates, and mixtures thereof, but especially the salts of weak organic or inorganic acids, such as carbonates, acetates, formates and cyanides. Cesium compounds are preferred. The salts used can be generated in the reaction vessel from the hydroxide and the corresponding acid or from suitable acid derivatives.

ハロゲンニトロベンゼン１モル当り0.05〜５
ｇ、好ましくは0.1〜１ｇの炭酸セシウムに相当
するモル量でルビジウム及びセシウム化合物を加
える。 0.05 to 5 per mole of halogen nitrobenzene
Rubidium and cesium compounds are added in molar amounts corresponding to g, preferably 0.1 to 1 g of cesium carbonate.

当量または当量の1.5倍まで過剰の炭酸カリウ
ムを用いることができる。 An equivalent or up to 1.5 times the equivalent excess of potassium carbonate can be used.

反応中に生じる水を同伴剤を用いる蒸留により
反応混合物から除去することが有利である。例え
ば次のものが同伴剤として含まれる：キシレン、
トルエン、ベンゼン、クロロベンゼン、クロロト
ルエン、アニリン及び／またはトルイジン、好ま
しくはキシレンまたはトルエン。 It is advantageous to remove the water formed during the reaction from the reaction mixture by distillation using an entraining agent. For example, the following may be included as entraining agents: xylene,
Toluene, benzene, chlorobenzene, chlorotoluene, aniline and/or toluidine, preferably xylene or toluene.

必要に応じて、希釈剤、例えば不活性有機炭化
水素の存在下、例えばキシレンの存在下において
本発明の方法を行うことができる。更に、溶媒と
して芳香族第一級アミンそれ自体を用いることが
できる。 If desired, the process of the invention can be carried out in the presence of a diluent, such as an inert organic hydrocarbon, such as xylene. Furthermore, the aromatic primary amine itself can be used as a solvent.

本法の反応温度は広範囲に定めることができ
る。この温度は一般的に140〜225℃、好ましくは
180〜210℃である。 The reaction temperature of this method can be set within a wide range. This temperature is generally 140-225℃, preferably
The temperature is 180-210℃.

本法は通常の方法により連続的にか、または非
連続的に行うことができる。 The process can be carried out continuously or discontinuously by conventional methods.

同様に、異なつた方法により反応混合物を処理
することができる。反応混合物中の塩は昇温下の
遠心分離またはロ過により物理的に分離すること
ができる。温キシレンでの洗浄後、及び乾燥後
に、薄い灰色の粉末状固体物質が残る。未反応の
ハロゲンニトロベンゼン及び第一級芳香族アミン
は水蒸気を用いてロ液から除去することができ、
その際に大部分のニトロジフエニルアミンは粒状
物質として生じる。他の可能性としては真空下で
ロ液を部分的に蒸留し、そして次に生成物を残渣
中に得ること、または結晶化により実質的に４−
ニトロジフエニルアミンを分離し、そして／また
は沈殿剤、例えばキシレンとロ液を混合すること
がある。この場合、４−ニトロジフエニルアミン
を極めて純粋な状態で生成し、そしてこの条件で
直接更に処理することができる。 It is likewise possible to work up the reaction mixture in different ways. Salts in the reaction mixture can be physically separated by centrifugation or filtration at elevated temperatures. After washing with hot xylene and drying, a light gray powdery solid material remains. Unreacted halogen nitrobenzene and primary aromatic amine can be removed from the filtrate using steam;
Most of the nitrodiphenylamine is produced as particulate material. Other possibilities include partially distilling the filtrate under vacuum and then obtaining the product in the residue, or by crystallization substantially 4-
The nitrodiphenylamine may be separated and/or the filtrate mixed with a precipitating agent, such as xylene. In this case, 4-nitrodiphenylamine is produced in extremely pure form and can be further processed directly under these conditions.

銅触媒はくり返し使うことができる。十分な活
性を達成させるために、通常使用される量より少
ない量の触媒を場合によつては新たな状態で加え
る。副生物を除去するために、生じた母液の一部
を必要に応じて分離する。塩を除去するために、
好ましくは昇温下（85〜95℃）で塩を溶解させる
に必要な水の量で反応混合物を撹拌処理すること
もできる。相分離後、例えば水蒸気蒸留による
か、または４−ニトロジフエニルアミンより容易
に揮発する成分を除去することにより有機層を更
に処理する。 Copper catalysts can be used repeatedly. In order to achieve sufficient activity, a smaller amount of catalyst than is normally used is added, if necessary in fresh form. A portion of the resulting mother liquor is optionally separated to remove by-products. To remove salt,
The reaction mixture can also be stirred with the amount of water necessary to dissolve the salt, preferably at elevated temperature (85-95°C). After phase separation, the organic layer is further processed, for example by steam distillation or by removing components that are more easily volatile than 4-nitrodiphenylamine.

本法により、短かい反応時間中に85％以上の収
率及び高い純度で４−ニトロジフエニルアミンを
生成することができる。この方法において副生物
は少量程度のみで生じる。 By this method, 4-nitrodiphenylamine can be produced with a yield of more than 85% and high purity in a short reaction time. In this process, by-products are produced only in small amounts.

本発明の方法により生じる４−ニトロジフエニ
ルアミンを公知の方法で容易にアミノジフエニル
アミンに還元することができ、そしてこれらのも
のはそのままでも例えば染料またはゴムに対する
安定性の製造における価値ある中間体生成物であ
る（米国特許第3163616号参照）。 The 4-nitrodiphenylamines produced by the process of the invention can be easily reduced to aminodiphenylamines by known methods, and these as such are valuable intermediates in the production of e.g. dyes or rubber-stability compounds. (see US Pat. No. 3,163,616).

実施例 １ ４−クロロニトロベンゼン１モル、アニリン
1.9モル、乾燥した炭酸カリウム1.25モル、酸化
銅（）1/42モル、乾燥した炭酸セシウム1/950
モル及びキシレン1/10モルを撹拌機及び水分離器
を有する分離カラムを備えた容量２の三ツ口フ
ラスコ中に400r.p.mの撹拌速度で導入した。Example 1 1 mol of 4-chloronitrobenzene, aniline
1.9 mol, dry potassium carbonate 1.25 mol, copper oxide () 1/42 mol, dry cesium carbonate 1/950
mol and 1/10 mol of xylene were introduced at a stirring speed of 400 rpm into a three-necked flask of capacity 2 equipped with a separation column with a stirrer and a water separator.

撹拌しながら反応混合物を195℃に加熱した。
10〜10.5mlの水が分離されるまでフラスコの内容
物をこの温度に保持し、そして試料の４−クロロ
ニトロベンゼン含有量を液体クロマトグラフイー
で測定した。この含有量が最初の量の1.5％より
少ない場合、冷却して反応を停止させた。それ以
外はこの値が得られるまで反応を続けた。完全な
反応の期間は５〜６時間であつた。 The reaction mixture was heated to 195°C while stirring.
The contents of the flask were held at this temperature until 10-10.5 ml of water had been separated and the 4-chloronitrobenzene content of the sample was determined by liquid chromatography. If this content was less than 1.5% of the initial amount, the reaction was stopped by cooling. Otherwise, the reaction was continued until this value was obtained. The duration of complete reaction was 5-6 hours.

水50mlを100℃で加え、そして揮発成分を水蒸
気を用いて除去した。フラスコの内容物の水相を
分離し、そして冷却しながら有機相を固化した。
灰色−緑色の粒状物質216ｇが得られ、このもの
は液体クロマトグラフイーによる分析によれば４
−クロロニトロベンゼンを基準として87％の収率
に対応する86重量％の４−ニトロジフエニルアミ
ンを含んでいた。 50 ml of water were added at 100°C and volatile components were removed using steam. The aqueous phase of the flask contents was separated and the organic phase solidified while cooling.
216 g of gray-green particulate material was obtained, which according to liquid chromatography analysis
- It contained 86% by weight of 4-nitrodiphenylamine, corresponding to a yield of 87%, based on chloronitrobenzene.

実施例 ２ 炭酸セシウムの代りにシアン化セシウム1/930
モルを用いて実施例１をくり返して行つた。Example 2 Cesium cyanide 1/930 instead of cesium carbonate
Example 1 was repeated using mol.

用いた４−クロロニトロベンゼンを基準として
88.7％の収率で４−ニトロジフエニルアミンが得
られた。 Based on the 4-chloronitrobenzene used
4-nitrodiphenylamine was obtained with a yield of 88.7%.

実施例 ３ アニリン1.95モル、炭酸カリウム1.3モル、酸
化銅（）1/45モル、酢酸セシウム1/850モル、
水1/20モル及びキシレン1/12モルを用いる以外は
前の通り実施例１の方法を行つた。約11mlの水を
除去した。４−ニトロジフエニルアミンの収率は
４−ニトロクロロベンゼンを基準として89.2％で
あつた。Example 3 1.95 mol of aniline, 1.3 mol of potassium carbonate, 1/45 mol of copper oxide (), 1/850 mol of cesium acetate,
The procedure of Example 1 was carried out as before except that 1/20 mole of water and 1/12 mole of xylene were used. Approximately 11 ml of water was removed. The yield of 4-nitrodiphenylamine was 89.2% based on 4-nitrochlorobenzene.

実施例 ４ 実施例１において1/950モルの炭酸セシウムの
代りに1/950モルの酢酸ルビジウムを用い実施例
１を繰り返した。７時間の反応時間の後、４−ニ
トロ−ジフエニルアミンが85％の収率で得られ
た。Example 4 Example 1 was repeated using 1/950 mole rubidium acetate instead of 1/950 mole cesium carbonate. After a reaction time of 7 hours, 4-nitro-diphenylamine was obtained with a yield of 85%.

実施例 ５ 実施例１において1/950モルの炭酸セシウムの
代りに1/1500モルの乳酸（Iactate）セシウム及
び1/1500モルの炭酸ルビジウムよりなる混合物を
用い実施例１を繰り返した。５時間の反応時間の
後、４ニトロ−ジフエニルアミンが89％の収率で
得られた。Example 5 Example 1 was repeated using a mixture of 1/1500 mol of cesium lactate and 1/1500 mol of rubidium carbonate instead of 1/950 mol of cesium carbonate. After a reaction time of 5 hours, 4 nitro-diphenylamine was obtained with a yield of 89%.

Claims (1)

【特許請求の範囲】 １ ハロゲンニトロベンゼン１モルを基準として
炭酸カリウム１〜1.5当量及び銅化合物0.001〜0.1
モルの存在における４−ニトロハロゲンベンゼン
と第一級芳香族アミンとの反応による４−ニトロ
ジフエニルアミンの製造方法であつて、ハロゲン
ニトロベンゼン１モル当り0.1582〜15.82モルの
ルビジウム化合物および／またはセシウム化合物
を添加する製造方法。 ２ ４−ニトロジフエニルアミンが式 式中、R1、R2、R3及びR4は同一または相異な
るものであり、且つ水素または炭素原子１〜９個
を有するアルキル基である、 に対応することを特徴とする、特許請求の範囲第
１項記載の方法。 ３ ４−ニトロクロロベンゼンをアニリンと反応
させ、４−ニトロジフエニルアミンを生成するこ
とを特徴とする、特許請求の範囲第１項記載の方
法。 ４ ルビジウムまたはセシウム化合物として、弱
い有機または無機酸の塩を用いることを特徴とす
る、特許請求の範囲第１項記載の方法。 ５ セシウム化合物を用いることを特徴とする、
特許請求の範囲第１項又は第４項記載の方法。 ６ 各々の場合に、用いるハロゲンニトロベンゼ
ン１モルを基準として、炭酸セシウム0.1〜１ｇ
に相当するモル量でルビジウムまたはセシウム化
合物を用い、そして0.01〜0.05モルの量で銅触媒
を用いることを特徴とする、特許請求の範囲第１
項記載の方法。 ７ 反応を140〜225℃で行うことを特徴とする、
特許請求の範囲第１項記載の方法。 ８ 反応を180〜210℃で行うことを特徴とする、
特許請求の範囲第１項記載の方法。 ９ 反応中に生じる水を同伴剤（entrainer）を
用いる上流で除去することを特徴とする、特許請
求の範囲第１項記載の方法。[Claims] 1. 1 to 1.5 equivalents of potassium carbonate and 0.001 to 0.1 equivalent of copper compound based on 1 mole of halogen nitrobenzene.
A process for producing 4-nitrodiphenylamine by reaction of 4-nitrohalogenbenzene with a primary aromatic amine in the presence of 0.1582 to 15.82 mol of rubidium and/or cesium compounds per mole of halogennitrobenzene. A manufacturing method that involves adding. 2 4-Nitrodiphenylamine has the formula A claim characterized in that R 1 , R 2 , R 3 and R 4 are the same or different and correspond to hydrogen or an alkyl group having 1 to 9 carbon atoms. The method described in item 1. 3. Process according to claim 1, characterized in that 4-nitrochlorobenzene is reacted with aniline to produce 4-nitrodiphenylamine. 4. The method according to claim 1, characterized in that a salt of a weak organic or inorganic acid is used as the rubidium or cesium compound. 5 Characterized by using a cesium compound,
A method according to claim 1 or 4. 6 In each case 0.1 to 1 g of cesium carbonate, based on 1 mole of halogen nitrobenzene used.
Claim 1, characterized in that a rubidium or cesium compound is used in a molar amount corresponding to
The method described in section. 7. Characterized by carrying out the reaction at 140-225°C,
A method according to claim 1. 8. Characterized by carrying out the reaction at 180 to 210°C,
A method according to claim 1. 9. Process according to claim 1, characterized in that the water formed during the reaction is removed upstream using an entrainer.
JP58231624A 1982-12-14 1983-12-09 Manufacture of 4-nitrodiphenylamine Granted JPS59112947A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19823246151 DE3246151A1 (en) 1982-12-14 1982-12-14 Process for the preparation of 4-nitrodiphenylamines
DE3246151.8 1982-12-14

Publications (2)

Publication Number Publication Date
JPS59112947A JPS59112947A (en) 1984-06-29
JPS6323184B2 true JPS6323184B2 (en) 1988-05-16

Family

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Country Link
JP (1) JPS59112947A (en)
KR (1) KR910002370B1 (en)
BR (1) BR8306844A (en)
CS (1) CS236898B2 (en)
DD (1) DD215536A5 (en)
DE (1) DE3246151A1 (en)
IN (1) IN160179B (en)
SU (1) SU1158038A3 (en)

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* Cited by examiner, † Cited by third party
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DE19942394C1 (en) 1999-09-06 2001-02-01 Bayer Ag Increasing the yield of nitrodiphenylamines in base/palladium-catalysed nitrohalobenzene/aromatic amine reactions by using a base which has been milled and optionally also dried
DE10005601A1 (en) 2000-02-09 2001-08-16 Bayer Ag Process for the preparation of aminodiphenylamines
DE10300126A1 (en) * 2003-01-07 2004-07-15 Bayer Aktiengesellschaft Process for the preparation of aminodiphenylamines
DE10300125A1 (en) 2003-01-07 2004-07-15 Bayer Ag Process for the preparation of nitrodiphenylamines
RU2502724C1 (en) * 2012-10-22 2013-12-27 Российская Федерация, От Имени Которой Выступает Министерство Промышленности И Торговли Российской Федерации Method of producing nitrodiphenylamines

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5495523A (en) * 1977-12-27 1979-07-28 Monsanto Co Manufacture of nitrodiaryl amines
JPS54128533A (en) * 1978-03-13 1979-10-05 Monsanto Co Manufacture of nitrodiarylamines

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL211629A (en) * 1955-12-07
DE1056619B (en) * 1956-11-29 1959-05-06 Bayer Ag Process for the preparation of 4-nitro-diarylamines
DE1090225B (en) * 1957-11-05 1960-10-06 Us Rubber Co Process for the preparation of p-nitrodiphenylamines
US3155727A (en) * 1960-07-25 1964-11-03 Goodyear Tire & Rubber Reaction of aromatic amines with para halo nitrobenzenes using copper cyanide condensation catalyst
US3313854A (en) * 1961-11-20 1967-04-11 Universal Oil Prod Co Preparation of para-nitrodiphenylamines utilizing a copper oxide catalyst
US3277175A (en) * 1963-11-26 1966-10-04 Eastman Kodak Co Preparation of p-nitrodiphenylamines
US4187248A (en) * 1977-11-23 1980-02-05 Monsanto Company Making a nitrodiarylamine by reacting an alkali metal salt of a formamide with a nitrohaloarene
US4187249A (en) * 1977-12-27 1980-02-05 Monsanto Company Promoting the reaction of sodium salts of formyl derivatives of aromatic amines to form nitrodiarylamines

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5495523A (en) * 1977-12-27 1979-07-28 Monsanto Co Manufacture of nitrodiaryl amines
JPS54128533A (en) * 1978-03-13 1979-10-05 Monsanto Co Manufacture of nitrodiarylamines

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BR8306844A (en) 1984-07-24
JPS59112947A (en) 1984-06-29
KR840007560A (en) 1984-12-08
DE3246151C2 (en) 1988-06-30
CS236898B2 (en) 1985-05-15
IN160179B (en) 1987-06-27
DE3246151A1 (en) 1984-06-14
SU1158038A3 (en) 1985-05-23
DD215536A5 (en) 1984-11-14
KR910002370B1 (en) 1991-04-20

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